The present invention relates to a novel method for thermal spray coating and a rare earth oxide powder used therefor or, more particularly, to a method for thermal spray coating capable of giving a highly heat-resistant, abrasion-resistant and corrosion-resistant coating layer on the surface of a variety of substrates and a rare earth oxide powder having unique granulometric parameters and suitable for use as a thermal spray coating material.
The method of so-called thermal spray coating utilizing a gas flame or plasma flame is a well established process for the formation of a coating layer having high heat resistance, abrasion resistance and corrosion resistance on the surface of a variety of substrate articles such as bodies made from metals, concrete, ceramics and the like, in which a powder to form the coating layer is ejected or sprayed as being carried by a flame at the substrate surface so that the particles are melted in the flame and deposited onto the substrate surface to form a coating layer solidified by subsequent cooling.
The powder to form the coating layer on the substrate surface by the thermal spray coating method, referred to as a thermal spray powder hereinafter, is prepared usually by melting a starting material in an electric furnace and solidifying the melt by cooling followed by crushing, pulverization and particle size classification to obtain a powder having a controlled particle size distribution suitable for use in process of thermal spray coating.
A typical industrial field in which the method of thermal spray coating is widely employed is the semiconductor device manufacturing process which in many cases involves a plasma etching or plasma cleaning process by using a chlorine- and/or fluorine-containing etching gas utilizing the high reactivity of the plasma atmosphere of the halogen-containing gas. Examples of the fluorine- and/or chlorine-containing gases used for plasma generation include SF6, CF4, CHF3, ClF3, HF, Cl2, BCl3 and HCl either singly or as a mixture of two kinds or more. Plasma is generated when microwaves or high-frequency waves are introduced into the atmosphere of these halogen-containing gases. It is therefore important that the surfaces of the apparatus exposed to these halogen-containing gases or plasma thereof are highly corrosion-resistant. In the prior art, members or parts of such an apparatus are made from or coated by thermal spray coating with various ceramic materials such as silica, alumina, silicon nitride, aluminum nitride and the like in consideration of their good corrosion resistance.
Usually, the above mentioned ceramic materials are used in the form of a thermal spray powder prepared by melting, solidification, pulverization and particle size classification of the base ceramic material as a feed to a gas thermal spray or plasma thermal spray coating apparatus. It is important here that the particles of the thermal spray powder are fully melted within the gas flame or plasma flame in order to ensure high bonding strength of the thermal spray coating layer to the substrate surface.
It is also important here that the thermal spray powder has good flowability in order not to cause clogging of the feed tubes for transportation of the powder from a powder reservoir to a thermal spray gun or the spray nozzle because smoothness of the powder feeding rate is a very important factor affecting the quality of the coating layer formed by the thermal spray coating method in respect of the heat resistance, abrasion resistance and corrosion resistance. In this regard, the thermal spray powders used in the prior art are generally unsatisfactory because the particles have irregular particle configurations resulting in poor flowability with a large angle of repose so that the feed rate of the powder to the thermal spray gun cannot be increased as desired without causing clogging of the spray nozzle so that the coating process cannot be conducted smoothly and continuously greatly affecting the productivity of the process and quality of the coating layer.
With an object to obtain a thermal spray coating layer having increased denseness and higher hardness, furthermore, a method of reduced-pressure plasma thermal spray coating is recently proposed in which the velocity of thermal spraying can be increased but the plasma flame is necessarily expanded in length and cross section with a decreased energy density of the plasma flame so that, unless the thermal spray powder used therein has a decreased average particle diameter, full melting of the particles in the flame cannot be accomplished. While a thermal spray powder having a very small average particle diameter is prepared, as is mentioned above, by melting the starting material, solidification of the melt, pulverization of the solidified material and particle size classification, the last step of particle size classification by screening can be conducted only difficulties when the average particle diameter of the powder is already very small.
While in the prior art, many of the parts or members of a semiconductor-processing apparatus are made from a glassy material or fused silica glass, these materials have only low corrosion resistance against a plasma atmosphere of a halogen-containing gas resulting not only rapid wearing of the apparatus but also a decrease in the quality of the semiconductor products as a consequence of surface corrosion of the apparatus by the halogen-containing plasma atmosphere.
Although ceramic materials such as alumina, aluminum nitride and silicon carbide are more resistant than the above mentioned glassy materials against corrosion in a plasma atmosphere of a halogen-containing gas, a coating layer of these ceramic materials formed by the method of thermal spray coating is not free from the problem of corrosion especially at an elevated temperature so that semiconductor-processing apparatuses made from or coated with these ceramic materials have the same disadvantages as mentioned above even if not so serious.
The present invention accordingly has an object, in order to overcome the above described problems and disadvantages in the prior art methods of thermal spray coating, to provide a novel and improved method of thermal spray coating which can be conducted at a high productivity of the process by using a thermal spray powder having excellent flowability in feeding and good fusibility in the flame and capable of giving a coating layer with high corrosion resistance against a halogen-containing gas or a plasma atmosphere of a halogen-containing gas even at an elevated temperature.
Thus, the present invention provides a method for the formation of a highly corrosion-resistant coating layer on the surface of a substrate by thermal spray coating, which comprises the step of: spraying particles of a rare earth oxide or a rare earth-based composite oxide, in which the impurity content of an iron group element or, in particular, iron does not exceed 5 ppm by weight calculated as oxide, at the substrate surface as being carried by a flame or, in particular, plasma flame to deposit a melt of the particles onto the substrate surface forming a layer. It is further desirable that the contents of alkali metal elements and alkaline earth metal elements as impurities in the rare earth oxide-based thermal spray powder each does not exceed 5 ppm by weight calculated as the respective oxides.
In particular, the particles of the rare earth oxide or rare earth-based composite oxide have an average particle diameter in the range from 5 to 80 xcexcm with a dispersion index in the range from 0.1 to 0.7 and a specific surface area in the range from 1 to 5 m2/g. More particularly, the particles are preferably granules of a globular configuration obtained by granulation of primary particles of the oxide having an average particle diameter in the range from 0.05 to 10 xcexcm.
It is more desirable that the above described rare earth oxide-based thermal spray powder has the granulometric characteristics including;
a globular particle configuration with an aspect ratio of the particles not exceeding 2;
a particle diameter D90 at 90% by weight level in the particle diameter distribution not exceeding 60 xcexcm;
a bulk density not exceeding 1.6 g/cm3; and
a cumulative pore volume of at least 0.02 cm3/g for the pores having a pore radius not exceeding 1 xcexcm.
The thermal spray powder used in the inventive method of thermal spray coating consists of particles of an oxide of a rare earth element or a composite oxide of a rare earth element and another element such as aluminum, silicon and zirconium. It is essential that the impurity content of iron group elements. i.e. iron, cobalt and nickel, in the powder does not exceed 5 ppm by weight calculated as oxide. The particles of the thermal spray powder, which are preferably granulated particles, should preferably have specified values of several granulometric parameters including the average particle diameter, dispersion index for the particle diameter distribution, globular particle configuration defined in terms of the aspect ratio of particles, bulk density, pore volume and specific surface area as obtained by granulation of primary particles of the oxide having a specified average particle diameter.
When a thermal spray powder satisfying the above mentioned various requirements is used in the inventive method, the coating layer of the rare earth oxide or rare earth-based composite oxide has very desirable properties of high heat resistance, abrasion resistance and corrosion resistance as well as in respect of uniformity of the coating layer and adhesion of the coating layer to the substrate surface if not to mention the greatly improved productivity of the coating process by virtue of the good flowability of the powder in feeding to the spray gun. When the content of iron impurity in the powder is too high, for example, it is a possible case that the iron impurity is locally concentrated to form speckles where iron reacts with the rare earth element to cause localized corrosion of the coating layer in an atmosphere of a halogen-containing gas or plasma thereof.
The above mentioned very low impurity content of the iron group elements can be accomplished by using a high-purity starting oxide material and conducting the granulation process of the starting oxide powder in an atmosphere of a high-class clean room in order to avoid entering of iron-containing dust into the oxide powder from the ambience.
The thermal spray powder used in the inventive method is not limited to an oxide or composite oxide of the rare earth element but can be a carbide, boride or nitride of the rare earth element although oxides are preferable in respect of the excellent chemical stability in an atmosphere of a halogen-containing gas or plasma thereof.
The rare earth element, of which a powder of oxide or composite oxide is employed as the thermal spray powder in the inventive method, includes yttrium and the elements having an atomic number in the range from 57 to 71, of which yttrium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium are preferable and yttrium, gadolinium, dysprosium, erbium and ytterbium are more preferable. These rare earth elements can be used either singly or as a combination of two kinds or more. The composite oxide of a rare earth element is formed from a rare earth element and a composite-forming element selected from aluminum, silicon and zirconium or, preferably, from aluminum and silicon. The chemical form of the composite oxide includes those expressed by the formulas RAlO3, R4Al2O9, R3Al5O12, R2SiO5, R2Si2O7, R2Zr2O7 and the like, in which R is a rare earth element, though not particularly limitative thereto. A mixture of a rare earth oxide powder and an oxide powder of aluminum, silicon and/or zirconium can also be used as an equivalent to the composite oxide powder since a composite oxide can be formed in the flame from the oxides when melted.
It is important that primary particles of a rare earth oxide or a rare earth-based composite oxide are granulated into granules having an average diameter in the range from 5 to 80 xcexcm or, preferably, from 20 to 80 xcexcm for use as a thermal spray powder having good flowability. Oxide granules having an average diameter smaller than 5 xcexcm are disadvantageous due to the difficulties encountered in the process of granulation while, when the average diameter of the granules is too large, fusion of the granules in the spraying flame is sometimes incomplete to leave the core portion of the granules unmelted resulting in a decrease of the adhesion of the coating layer to the substrate surface and decreased utilizability of the thermal spray powder.
It is also important that the granulated particles of the thermal spray powder have a particle diameter distribution as narrow as possible because, when the powder having a broad particle diameter distribution is exposed to a high temperature flame such as plasma flame, granules having a very small diameter are readily melted eventually to be lost by evaporation while granules having a great diameter are melted only incompletely leading to failure of deposition of the melt on the substrate surface resulting in the loss of the thermal spray powder. A problem in a thermal spray powder of a narrow particle size distribution is that the preparation process thereof is complicated not to be suitable for mass production of the powder. Thermal spray powders having a broad particle size distribution generally have poor flowability to cause clogging of the feed tubes and spray nozzles. In this regard, the thermal spray powder should have an appropriate value of dispersion index in the range from 0.1 to 0.7 for the particle diameter distribution. The dispersion index mentioned above is a value defined in terms of the equation:
Dispersion index=(D90xe2x88x92D10)/(D90+D10),
in which D90 and D10 are each such an upper limit particle diameter that 90% by weight or 10% by weight, respectively, of the particles constituting the powder have a diameter smaller than D90 and D10, respectively.
Since the thermal spray powder consists of granules of a relatively large average particle diameter as prepared by granulation of fine primary particles, the specific surface area of the granules can be relatively large for the relatively large particle diameter so as to ensure good fusing behavior in the thermal spray fusion. In consideration of the balance between advantages and disadvantages, the thermal spray powder used in the inventive method should desirably have a specific surface area in the range from 1 to 5 m2/g as measured by the BET method. When the specific surface area of the powder is too small, the efficiency of heat transfer to the granules in thermal spray fusion cannot be high enough resulting in occurrence of unevenness in the coating layer. On the other hand, a too large specific surface area of the granules means an undue fineness of the primary particles to cause inconvenience in handling of the powder.
In consideration of the above mentioned various requirements for the granules, the primary particles, from which the granules are prepared by granulation, of the rare earth oxide or rare earth-based composite oxide should have an average particle diameter in the range from 0.05 to 10 xcexcm or, preferably, from 0.5 to 10 xcexcm.
In addition to the above described several requirements, it is more desirable that the particles or granules of the thermal spray powder in the present invention satisfy various other granulometric characteristics including:
a globular particle configuration with an aspect ratio of the particles not exceeding 2;
a particle diameter D90 at 90% by weight level in the particle diameter distribution not exceeding 60 xcexcm;
a bulk density not exceeding 1.6 g/cm3; and
a cumulative pore volume of at least 0.02 cm3/g for the pores having a pore radius not exceeding 1 xcexcm.
The above mentioned aspect ratio of the particles, by which the globular configuration of the particles is defined, is the ratio of the largest diameter to the smallest diameter of the particles. This value can be determined from a scanning electron microscopic photograph of the particles. An aspect ratio of 1 corresponds to a true spherical particle configuration and a value thereof larger than 2.0 represents an elongated particle configuration. When the aspect ratio of the particles or granules exceeds 2.0, the powder hardly exhibits good flowability. In this regard, the aspect ratio should be as small as possible to be close to 1.
The D90 value in the particle diameter distribution of the particles or granules should be 60 xcexcm or smaller or, preferably, in the range from 20 to 60 xcexcm or, more preferably, in the range from 25 to 50 xcexcm. When this value is too large, fusion of the particles is sometimes incomplete in thermal spray coating resulting in a rugged surface of the flame-fusion coating film on the substrate surface. When the thermal spray powder consists of granules prepared by using an organic binder, thermal decomposition of the binder resin is eventually incomplete in a large granule leaving a carbonaceous decomposition product in the coating film as a contaminant.
The bulk density and the cumulative pore volume of the particles or granules are also parameters affecting the fusing behavior of the powder in thermal spray coating. In this regard, the bulk density of the particles should be 1.6 g/cm3 or smaller and the cumulative pore volume should be 0.02 cm3/g or larger or, preferably, in the range from 0.03 to 0.40 cm3/g. When the bulk density is too large or the cumulative pore volume is too small, thermal spray fusion of the granules is sometimes incomplete resulting in degradation of the thermal spray coating films.
A typical procedure for granulation of the above described primary particles is as follows. Thus, the powder of primary particles is admixed with a solvent such as water and alcohol containing a binder resin to give a slurry which is fed to a suitable granulator machine such as rotary granulators, spray granulators, compression granulators and fluidization granulators to be converted into globular granules as an agglomerate of the primary particles, which are, after drying, subjected to calcination in atmospheric air for 1 to 10 hours at a temperature in the range from 1200 to 1800xc2x0 C. or, preferably, from 1500 to 1700xc2x0 C. to give a thermal spray powder consisting of globular granules having an average diameter of 5 to 80 xcexcm.
When granules of a rare earth-based composite oxide are desired as the thermal spray powder, it is of course a possible way that primary particles of the rare earth-based composite oxide are subjected to the above described procedure of granulation. Alternatively, it is also possible to employ, instead of the primary particles of the composite oxide, a mixture of primary particles of a rare earth oxide and a composite-forming oxide such as alumina, silica and zirconia in a stoichiometric proportion corresponding to the chemical composition of the composite oxide. When granules of a rare earth aluminum garnet of the formula R3Al5O12 are desired, for example, primary particles of the rare earth aluminum garnet can be replaced with a mixture of the rare earth oxide R2O3 particles and alumina Al2O3 particles in a molar ratio of 3:5.
Examples of the binder resin used in the granulation of the primary oxide particles into granules include polyvinyl alcohol, cellulose derivatives, e.g., carboxymethyl cellulose, hydroxypropylcellulose and methylcellulose, polyvinyl pyrrolidone, polyethyleneglycol, polytetrafluoroethylene resins, phenol resins and epoxy resins, though not particularly limitative thereto. The amount of the binder resin used for granulation is in the range from 0.1 to 5% by weight based on the amount of the primary oxide particles.
The process of thermal spray coating by using the above described oxide granules is conducted preferably by way of plasma thermal spraying or reduced-pressure plasma thermal spraying by using a gas of argon or nitrogen or a gaseous mixture of nitrogen and hydrogen, argon and hydrogen, argon and helium or argon and nitrogen, though not particularly limitative thereto.
The method of thermal spray coating according to the invention is applicable to a variety of substrates of any materials without particular limitations. Examples of applicable materials of substrates include metals and alloys such as aluminum, nickel, chromium, zinc and zirconium as well as alloys of these metals, ceramic materials such as alumina, zirconia, aluminum nitride, silicon nitride and silicon carbide, and fused silica glass. The thickness of the coating layer formed by the thermal spray coating method is usually in the range from 50 to 500 xcexcm depending on the intended application of the coated articles. Members and parts of a semiconductor processing apparatus exhibiting high performance can be obtained by coating according to the inventive method.
Since the thermal spray powder used in the inventive method consists of globular granules of fine primary particles of the oxide, the powder can be smoothly sprayed into the flame without clogging of the spray nozzles and the granules can be melted in the plasma flame with high efficiency of heat transfer so that the coating layer formed by the method has a very uniform and dense structure. The impurity limitation of the thermal spray powder that the content of the iron group elements does not exceed 5 ppm by weight as oxides is particularly important for obtaining a coating layer free from localized corrosion even against the plasma of a halogen-containing etching gas sometimes encountered in a semiconductor processing apparatus. The thermal spray coated layer according to the present invention can be imparted with still improved quality when the thermal spray powder contains alkali metal elements and alkaline earth metal elements as impurities each group in an amount not exceeding 5 ppm by weight calculated as oxides.
In the following, the method of the present invention for thermal spray coating is described in more detail by way of Examples and Comparative Examples, which, however, never limit the scope of the invention in any way. In the Examples below, the values of particle size distribution D10, D50 and D90 were determined by using an instrument Microtrac Particle Size Analyzer Model 9220 FRA.